Grafted polymers as oleophobic low adhesion anti-wetting coatings

ABSTRACT

An oleophobic grafted polymer includes a crosslinked fluoroelastomer and a perfluorinated polyether grafted to the crosslinked fluoroelastomer. A process for making an oleophobic grafted polymer includes crosslinking a fluoroelastomer with an aminofunctionalized silane and grafting an alkoxysilane-terminated perfluorinated polyether to the crosslinked fluoroelastomer.

STATEMENT OF RELATED APPLICATIONS

This application is a continuation-in-part of U.S. application Ser. No. 13/931,983, filed Jun. 30, 2013, the entire contents of which are incorporated herein by reference in its entirety.

BACKGROUND

Embodiments disclosed herein relate to coatings. In particular, embodiments disclosed herein relate to oleophobic anti-wetting coatings employed in various applications, such as on the front face of a printhead and other surfaces that benefit from low adhesive anti-wetting characterstics.

In typical solid ink printhead configurations, a nozzle plate is provided with an array of jets through which the ink exits a jet stack. In some printhead systems, the nozzle plate and jet stacks comprise stainless steel plates, although recently these parts have been replaced with flexible, polymer layers such as polyimides. In some instances, the polyimide film receives an anti-wetting coating, bonded to a stainless steel aperture plate, and subsequently a laser ablates the array of apertures into the polyimide film.

Drooling nozzles, wetting and adhesion of ink on the printhead front face lead to missing and misdirectional jetting along with poor image quality. Drooling nozzles weep ink when the internal pressure of the printhead exceeds a particular pressure. The higher the pressure the nozzles can maintain without weeping the better the performance. Wetting occurs when the front face of the printhead remains wet after printing. This ink that remains on the printhead can block the nozzles resulting in missing nozzles and misdirectional printing. FIG. 1 shows a photograph of such a contaminated printhead.

One approach to address these issues employs an active cleaning blade system. The system purges ink from the printhead and a wiper blade then wipes the ink off of the front face. Ink purges typically occur after the system detects missing jets and after a power-down when the ink has frozen or solidified, shrunk and drawn air into the system. The ink purge expels contamination, trapped air and clears the nozzles, and then the wipers clean off the front face.

In conjunction with wiper blade systems, various anti-wetting coatings have been used to improve performance. Current coatings, while having good thermal and ink stabilities, may suffer from lower mechanical robustness than may be desirable, especially with the demands placed on such coatings when used in conjunction with wiper blade systems. Other issues may arise due to coating stability under printhead manufacturing conditions.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows a photograph of a contaminated printhead front face.

FIG. 2 shows a side view of printhead assembly.

FIG. 3 shows a side view of an intermediate structure in a process for preparing the printhead assembly of FIG. 2, in accordance with embodiments disclosed herein.

FIG. 4 shows a side view of another intermediate structure in a process for preparing the printhead assembly of FIG. 2, in accordance with embodiments disclosed herein.

FIG. 5 shows a side view of yet another intermediate structure in a process for preparing the printhead assembly of FIG. 2, in accordance with embodiments disclosed herein.

FIG. 6 shows a synthetic procedure for making grafts.

FIG. 7 shows a thermogravimetric analysis (TGA) profile of an exemplary oleophobic grafted polymer, in accordance with embodiments disclosed herein. The TGA analysis indicates that the coating is thermally stable up to about 330° C. without weight loss.

SUMMARY

In some aspects, embodiments disclosed herein relate to oleophobic grafted polymers comprising a crosslinked fluoroelastomer and a perfluorinated polyether grafted to the crosslinked fluoroelastomer.

In some aspects, embodiments disclosed herein relate to processes for making oleophobic grafted polymers comprising crosslinking a fluoroelastomer with an aminofunctionalized silane and grafting an alkoxysilane-terminated perfluorinated polyether to the crosslinked fluoroelastomer.

In some aspects, embodiments disclosed herein relate to oleophobic grafted polymers comprising a crosslinked fluoroelastomer of structure:

wherein n is an integer from 1-10, each of R₁ and R₂ are independently an optionally fluorinated C₁-C₆ alkyl, and a perfluorinated polyether grafted to the crosslinked fluoroelastomer, wherein the OCH₃ groups of the polysiloxane crosslinker provide the reactive site for grafting the perfluorinated polyether.

DETAILED DESCRIPTION

Embodiments disclosed herein provide thermally stable, mechanically robust, low adhesion coatings based on oleophobic grafted polymers prepared by grafting crosslinked fluoroelastomers with perfluoropolyethers. The oleophobic grafted polymers may exhibit advantageous and/or complementary chemistry relative to polyurethane based coatings. In embodiments, the oleophobic grafted polymers employed as coatings may be particularly useful in high definition (HD) piezo printhead applications where the coating is applied on the printhead front face. Coatings (or films) of the oleophobic grafted polymers disclosed herein may exhibit high ink contact angles (greater than 50 degrees) and low sliding angles (less than 30 degrees) while having excellent thermal stability. In contrast to other coatings in the art, the oleophobic grafted polymers disclosed herein may produce little to no oil on the surface of the coating after curing. Moreover, such coatings may also exhibit minimmal thickness and mass loss after exposure to temperatures in excess of 290° C., making them suitable for use under stringent printhead fabrication conditions. Coatings employing the oleophobic grafted polymers disclosed herein are robust and may have a long shelf life even when subjected to continual exposure to temperatures of about 140° C. in molten ink for 2 days. The oleophobic grafted polymer coatings can be used with solid inks, pigmented inks and UV inks, and can enable good performance under high drool pressure while demonstrating easy clean and self-cleaning properties. Finally, the oleophobic grafted polymers can be formed into the requisite coatings by simple flow coating techniques, facilitating printhead manufacture. These and other advantages will be apparent to those skilled in the art.

In some embodiments, there are provided oleophobic grafted polymers comprising a crosslinked fluoroelastomer and a perfluorinated polyether grafted to the crosslinked fluoroelastomer.

As used herein, the term “oleophobic” when used in conjunction with the grafted polymers, refers to the physical property of the grafted polymers to repel oils, hydrocarbons, and more generally organic compounds, especially non-polar organic compounds. Oleophobic character imparts anti-wetting properties that are useful to repel wetting by solvent-based, solid inkjet based, and other pigmented and UV curable ink compositions. The oleophobic character can provide the coatings with good contact angle and sliding angle characteristics to to facilitate performance under high drool pressure.

As used herein, the term “grafted polymer” refers to the chemical joining of two or more pre-fabricated polymers. Grafting can be viewed as a form of polymer crosslinking. For example, a graft polymer disclosed herein may be prepared by reacting a pre-fabricated fluoroelastomer with a pre-fabricated perfluorinated polyether with the aid of a crosslinking agent. In embodiments, the crosslinker employed to crosslink the fluoroelastomer serves a dual role by providing a point of attachment for the graft chemistry to attach the perfluorinated polyether.

As used herein, the term “fluoroelastomer” refers to any material generally classified as an elastomer and containing a substantial degree of fluorination. Fluoroelastomers are synthetic fluorine-containing rubberlike polymers (typically co-polymers/terpolymers) characterized by high thermal stability, nonflammability, and resistance to corrosive media. In embodiments, the fluoroelastomer (FE) has a fluorine content of at least about 65 percent. In embodiments the fluorine content may be in a range from about 50 to about 90 percent, or about 60 to near 100 percent. Exemplary commercial fluoroelastomers generally have a fluorine content in a range from about 66 to about 70 percent.

Fluoroelastomers currently known and available include copolymers of vinylidene fluoride and hexafluoropropylene, terpolymers of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene, and alternating copolymers of propylene and tetrafluoroethylene. Such fluoroelastomers are available commercially as VITON™ (Dupont), DYNEON™ (3M), FLUOREL™ (3M), AFLAS™ (3M), and TECNOFLON™ (Solvay Solexis) classes of products. Such fluoroelastomers may exhibit excellent solvent and oil resistance and also have a relatively high temperature resistance compared to their non-fluorinated elastomer counterparts. In embodiments, the fluoroelastomer (FE) may be a polymer comprising a monomer unit selected from the group consisting of vinylidene fluoride, tetrafluorethylene, hexafluoropropylene, perfluoromethylvinylether and combinations thereof. In some such embodiments, the fluoroelastomer is a terpolymer of vinylidene fluoride, tetrafluorethylene, and hexafluoropropylene.

In embodiments, the fluoroelastomer (FE) has a molecular weight in a range from about 50,000 to about 70,000 daltons as measured by gel permeation chromatography. In embodiments the fluoroelastomer may be selected based on its tensile strength. In some such embodiments, the tensile strength of the fluoroelastomer may be in a range from about 15 mPa to about 25 mPa, or about 20 to about 25 mPa, or about 22 mPa to about 25 mPa, as measured by the standard ASTM D412C. In embodiments, the fluoroelastomer is selected particularly for its ability to participate in crosslinking chemistry as disclosed herein.

As used herein, a perfluorinated polyether refers to a polyether polymer having a substantial degree of fluorine substitution, and may be any fluorinated oligomer, homopolymer, or copolymer. Perfluorinated polyethers may exhibit comparable chemical stability to fluoroelastomers and may exhibit similar properties. In embodiments, the perfluorinated polyether (PFPE) is an alkoxysilane-terminated perfluorinated polyether having an average molecular weight in a range from about 1,500 daltons to about 2,500 daltons. Perfluorinated polyethers may be selected for their ability to bond to silanols, while having similar solvent repellent properties as the fluoroelastomers. Moreover, the perfluorinated polyether component may be selected to confer good abrasion resistance to the oleophobic grafted polymers. Abrasion resistance is especially useful in printhead systems employing wiper blades which will continually contact the coating during use.

Suitable perfluorinated polyethers include those of the FLUOROLINK™ (Solvay Solexis) class. In particular embodiments, the perfluorinated polyether may be bifunctionally substituted with a linker (L) terminating in an alkoxysilane as in the compound of general formula II:

Terminal alkoxysilane groups provide a chemical handle for downstream grafting chemistry, in accordance with embodiments disclosed herein. The grafting chemistry of the alkoxysilane group may be accomplished with a substrate bearing a hydroxyl group, such as an organic alcohol or a silanol. Silanol coupling partners provide access to siloxane products (Si—O—Si), such as the oleophobic grafted polymers disclosed herein. The linker (L) employed in compounds of formula II may comprise any substituted or unsubstituted C₁-C₆ alkyl, including fluorinated alkyls, such as perfluorinated alkyls. Linker L is also may also comprise any competent organic functional group to attach to the main perfluorinated polyether chain at a terminal oxygen, or in some embodiments, to at a terminal carbon atom. Non-limiting functional groups for attachment to oxygen include carbamates, esters, ethers, and the like. The R groups of the alkyoxysilane moiety (Si(OR)₃) may be the same or different. R may include methyl, ethyl, n-propyl, or isopropyl any of which may be substituted, including substitution with fluorine. R may also be hydrogen. In some embodiments, R is hydrogen after a hydrolysis step in preparation for grafting chemistry. In formula II, m, n, and o are integers that are selected based on the target molecular weight, as described above. In embodiments, m and o are integers from 2 to 8. In embodiments, n is an integer from 2 to 4.

In embodiments, the oleophobic grafted polymers disclosed herein may be compounds of formula I:

-   -   wherein FE is a fluoroelastomer,     -   PFPE is a perfluorinated polyether,     -   L is a linker,     -   m, n, and o are independently an integer from 1 to 10;     -   each incidence of R¹ and R² is independently an optionally         fluorinated C₁-C₆ alkyl,     -   R³ and R⁴ are independently an optionally fluorinated C₁-C₆         alkyl or an optionally fluorinated C₁-C₆ alkoxy. In embodiments,         m and o are independently an integer from 3 to 8 and n is an         integer from 1 to 10. In embodiments, the linker L comprises a         C₁-C₆ alkyl terminating in a functional group capable of         covalently linking to a terminal hydroxyl functionality group of         the perfluorinated polyether, as described above.

Any C₁-C₆ alkyl or C₁-C₆ alkoxy may be straight chain or branched. In embodiments, either of these groups may be optionally substituted, including substitution with halogens other than fluorine, such as chlorine or bromine. One skilled in the art will recognize that because structure I is polymeric, not every site where the perfluorinated polyether is shown in structure I may actually be so substituted. Thus, in embodiments, the printhead coatings disclosed herein may comprise a mixture of structure I and structure III:

where each of the groups are defined as set forth above. In embodiments, structure III may be a minor component and present at less than about 10 percent, or less than about 5 percent, or less than about 1 percent by weight of the coating composition. In some embodiments, compounds of structure III, where present, may have the latent silanol groups capped. For example, they may be capped as alkoxy groups by treatment with an alkylating agent.

Compounds of formula I comprise the fluorelastomers (FE) and perfluorinated polyethers (PFPE) described herein above. The two polymer types are brought together with the aid of a crosslinker. The crosslinker may be used to first crosslink the fluoroelastomer with itself. In embodiments, the fluoroelastomer is crosslinked with an aminofunctionalized silane. In embodiments, the aminofunctionalized silane also provides the graft attachment point for the perfluorinated polyether, as indicated in the structure I. In embodiments, the aminofunctionalized silane may be based on end-capping of a polysiloxane (or just siloxane where n=1 in structures I and III) with 3-aminopropyl trimethoxy silane (AO800, available from UCT, Bristol, Pa.). One skilled in the art will appreciate that the crosslinking agent may itself include a high degree of fluorination, although this is not necessary.

In embodiments, there are provided oleophobic grafted polymers comprising a crosslinked fluoroelastomer of structure A:

wherein n is an integer from 1-10, each of R₁ and R₂ are independently an optionally fluorinated C₁-C₆ alkyl, and a perfluorinated polyether grafted to the crosslinked fluoroelastomer, wherein the OCH₃ groups of the polysiloxane crosslinker provide the reactive site for grafting the perfluorinated polyether. In embodiments, the level of fluorination of optionally fluorinated C₁-C₆ alkyl can be any amount of fluorination, from a single fluorine up to perfluorinated, i.e., all hydrogens substituted by fluorine.

In some embodiments, there are provide processes for making an oleophobic grafted polymer comprising crosslinking a fluoroelastomer with an aminofunctionalized silane and grafting an alkoxysilane-terminated perfluorinated polyether to the crosslinked fluoroelastomer. In some such embodiments, the oleophobic grafted polymer accessed by such a process may comprise the compound of structure I, described above. In embodiments, the crosslinking step may be performed in the presence of the alkoxysilane-terminated perfluorinated polyether. Without being bound by theory, it is expected that the crosslinking of fluoroelastomer comprising hydrogen atoms in the backbone may allow the fluoroelastomer to be dehydrofluorinated as indicated in Step 1 of reaction Scheme 1 below. Dehydrofluorination provides an unsaturated fluoroelastomer intermediate and a protonated aminofucntionalized crosslinker. Regeneration of the amine with base (Step 2) and subsequent amine addition across the unsaturation (Step 3) provides a crosslinked fluoroelastomer which is ready to be grafted with the perfluorinated polyether. The grafting (Step 4) may be accomplished by hydrolyzing the alkoxy groups of the alkoxysilanes on the crosslinker and/or the alkoxysilane terminated perfluorinated polyether to provide the compounds of structure I.

Step 1: (Dehydrofluorination)

Step 2: (Regeneration of Amine)

Step 3: (Addition of Amine Across the Double Bond)

Step 4: (Hydrolysis and Condensation)

Scheme 1: Crosslinking reaction of a fluoroelastomer with an alkoxysilane terminated perfluorinated polyether using an aminofunctionalized fluorosilicone as a crosslinker.

As described above, the fluoroelastomer crosslinking step may be carried out in the presence of the perfluorinated polyether. In some such embodiments, a ratio of the aminofunctionalized silane to the alkoxysilane-terminated perfluorinated polyether is in a range from about 0.5:1 to about 3:1, or about 1:1 to about 2:1. In some embodiments, the ratio may be about 1.5:1. In embodiments, an amount of the aminofunctionalized silane relative to the fluoroelastomer is in a range from about 2 pph to about 10 pph. In embodiments, the attachment of the aminefunctionalized crosslinker with the perfluorinated polyether may be carried out before the crosslinking of the fluoroelastomer. Any of the steps describe above may be carried out with the aid of a catalyst and reactions may be optionally carried out at elevated temperatures. Typically, the reactions will be run in an organic solvent, such as methyl isobutyl ketone (MIBK). In embodiments, the reactions are all run in a one-pot sequence without isolation of chemical intermediates. In embodiments, the reaction products is used directly to form a coating with or with out any type of purification.

In some embodiments, there are provided inkjet printheads comprising a front face having a polymer coating, the polymer coating comprising an oleophobic grafted polymer comprising a crosslinked fluoroelastomer and a perfluorinated polyether grafted to the crosslinked fluoroelastomer. In some such embodiments, oleophobic grafted polymer comprises the compound of structure I.

Modeling has shown that the ink contact angle for competent oleophobic coating should be greater than about 40 degrees over lifespan of the coating to maintain a drool pressure specification of about 4 inches, with a higher contact angle being more beneficial. The front face coating ideally also has a low slide angle to enable the easy/self clean feature, which will lead to a printhead cartridge with no or low maintenance, high engine reliability and low run cost. Low slide angle is a measure of low ink adhesion and indicates that ink can be wiped off cleanly from the surface without leaving ink residue around the nozzle. Any ink residue around the nozzle area can break the ink meniscus and lead to drooling at pressure below the spec value. Also any coatings ideally maintain these properties after harsh fabrication conditions of the stacking press i.e., about 290° C. at 350 PSI for 30 min. Thus, in embodiments, the polymer coating has an ink contact angle of at least about 50 degrees and an ink slide angle of less than about 30 degrees. Furthermore, the polymer coating employed on the printhead front face may be characterized by being stable at 290° C. at 350 psi to facilitate manufacture.

The oleophobic low adhesion surface coating disclosed herein can be employed as an anti-wetting printhead front face coating for an inkjet printhead configured to eject ink onto a recording substrate. Any suitable recording substrate may be employed, including plain papers such as XEROX® 4024 papers, XEROX® Image Series papers, Courtland 4024 DP paper, ruled notebook paper, bond paper, silica coated papers such as Sharp Company silica coated paper, JuJo paper, Hammermill Laserprint Paper, and the like, transparency materials, fabrics, textile products, plastics, polymeric films, inorganic substrates such as metals and wood, and the like.

In some embodiments, the printhead comprises a front face having disposed on a surface thereof an oleophobic low adhesion coating comprising an oleophobic low adhesion polymeric material wherein jetted drops of ultra-violet gel ink or jetted drops of solid ink exhibit a contact angle with the surface coating that is greater than about 50 degrees. In some embodiments, the contact angle is greater than about 55, or greater than about 65 degrees. In one embodiment, there is no upper limit to the contact angle exhibited between the jetted drops of ultra-violet gel ink or jetted drops of solid ink and the surface coating. In another embodiment, the contact angle is less than about 150 degrees, or less than about 90 degrees. The greater the ink contact angle, the higher the drool pressure. Drool pressure relates to the ability of the aperture plate to avoid ink weeping out of the nozzle when the pressure of the ink tank (reservoir) increases. In some embodiments, the coatings provide, in combination, low adhesion and high contact angle for ultra-violet curable gel ink and solid ink which advantageously affects the drool pressure. In some embodiments, the coatings herein provide a low sliding angle of less than about 30 degrees. In some embodiments, the sliding angle is less than about 25 degrees. In some embodiments, the sliding angle is greater than about 1 degree. Contact angle is largely insensitive to drop size. However, contact angle can be measured upon disposing 5-10 microliter drops of UV ink or solid ink onto the surface coating. Sliding angle can be measured upon disposing 7-12 microliter drops of UV ink or solid ink onto the surface coating.

In embodiments described herein, the oleophobic low adhesion coatings are thermally stable, thereby providing a low sliding angle in a range from about 1 degree and about 30 degrees and a high contact angle in a range from about 45 degrees and about 150 degrees even after exposure to high temperatures (e.g., temperatures in a range from about 180° C. and about 325° C.) and high pressures (e.g., pressures in a range from about 100 psi and about 400 psi) for 15 extended periods of time (e.g., periods of time in a range from about 10 minutes and about 2 hours). In one embodiment, the oleophobic low adhesion coating is thermally stable after being exposed to a temperature of about 290° C. at pressures of about 350 psi for about 30 minutes. The fabrication of high density Piezo printheads requires a high temperature, high pressure adhesive bonding step. Hence, it would be desirable for a fronfface coating to withstand these high temperature and high pressure conditions. The stability of the oleophobic low adhesion surface coating described herein at high temperatures and high pressures is compatible with current printhead manufacturing processes.

When coated onto the front face of an inkjet printhead, the oleophobic low adhesion surface coating exhibits a sufficiently low adhesion with respect to the inks that are ejected from the inkjet printhead such that ink droplets remaining on the oleophobic low adhesion coating can slide off the printhead in a simple, self-cleaning manner. Contaminants such as dust, paper particles, etc., which are sometimes found on the front face of inkjet printheads, can be carried away from the inkjet printhead front face by a sliding ink droplet. Thus, the oleophobic low adhesion printhead front face coating can provide a self-cleaning, contamination-free inkjet printhead.

As used herein, the oleophobic low adhesion coating can exhibit a “sufficiently low wettability” with respect to inks that are ejected from an inkjet printhead when a contact angle between an ink and the oleophobic low adhesion coating is, in one embodiment, greater than about 50 degrees, or greater than about 55 degrees.

The oleophobic low adhesion coating disclosed herein can be employed as an oleophobic low adhesion printhead front face coating for an inkjet printhead of any suitable inkjet printer (e.g., continuous inkjet printers, thermal drop-on-demand (DOD) inkjet printers, and piezoeletric DOD inkjet printers). As used herein, the term “printer” encompasses any apparatus, such as a digital copier, bookmaking machine, facsimile machine, multi-function machine, and the like, which performs a print outputting function for any purpose.

The oleophobic low adhesion coating disclosed herein can be employed as an oleophobic low adhesion printhead front face coating for an inkjet printhead configured to eject any suitable ink (e.g., aqueous inks, solvent inks, UV-curable inks, dye sublimation inks, solid inks, etc.). An exemplary inkjet printhead suitable for use with the oleophobic low adhesion coating disclosed herein is described with respect to FIG. 2.

Referring to FIG. 2, an inkjet printhead 20 according to one embodiment of the 5 present invention includes a support brace 22, a nozzle plate 24 bonded to the support brace 22 and an oleophobic low adhesion coating, such as oleophobic low adhesion coating 26.

The support brace 22 is formed of any suitable material such as stainless steel and include apertures 22 a defined therein. The apertures 22 a may communicate with an ink source (not shown). The nozzle plate 24 may be formed of any suitable material such as polyimide and include nozzles 24 a defined therein. The nozzles 24 a may communicate with the ink source via the apertures 22 a such that ink from the ink source is jettable from the printhead 20 onto a recording substrate through a nozzle 24 a.

In the illustrated embodiment, the nozzle plate 24 is bonded to the support brace 22 by an intervening adhesive material 28. The adhesive material 28 may be provided as a thermoplastic adhesive can be melted during a bonding process to bond the nozzle plate 24 to the support brace 22. Typically, the nozzle plate 24 and the oleophobic low adhesion coating 26 are also heated during the bonding process. Depending on the material from which the thermoplastic adhesive is formed, bonding temperature can be in a range from about 180° C. and about 325° C.

Conventional oleophobic low adhesion coatings tend to degrade when exposed to temperatures encountered during typical bonding processes or other high-temperature, high pressure processes encountered during fabrication of inkjet printheads. However, the oleophobic low adhesion coating 26 disclosed herein exhibits a sufficiently low adhesion (indicated by low sliding angles) and high contact angle with respect to an ink after it has been heated to the bonding temperature. Thus, the oleophobic low adhesion coating 26 can provide a self-cleaning, contamination-free inkjet printhead 20 with high drool pressure. The ability of the oleophobic low adhesion coating 26 to resist substantial degradation in desirable surface properties (e.g., including low sliding angle and high contact angle) upon exposure to elevated temperatures enables inkjet printheads having self-cleaning abilities while maintaining high drool pressure, to be fabricated using high temperature and high pressure processes. An exemplary process of forming an inkjet 10 printhead is described with respect to FIGS. 2-5.

Referring to FIG. 3, an inkjet printhead, such as the inkjet printhead 20, may be formed by forming an oleophobic low adhesion coating, such as oleophobic low adhesion coating 26 on a substrate 32. The substrate 32 may be formed of any suitable material such as polyimide.

In one embodiment, the oleophobic low adhesion coating 26 may be formed on the substrate 32 by initially applying the reactant mixture that, as described above, includes at least one isocyanate and at least one perfluoropolyether compound. After the reactant mixture is applied to the substrate 32, the reactants are reacted together to form the oleophobic low adhesion coating 26. The reactants can be reacted together by, for example, curing the reactant mixture. In one embodiment, the reactant mixture is first cured at a temperature of about 130° C. for about 30 minutes to about 2 hours followed by a high temperature post-cure at about 290° C. for about 30 minutes to about 2 hours.

In one embodiment, the reactant mixture may be applied to the substrate 32 using any suitable method such as die extrusion coating, dip coating, spray coating, spin coating, flow coating, stamp printing, and blade techniques. An air atomization device such as an air brush or an automated air/liquid spray can be used to spray the reactant mixture. The air atomization device can be mounted on an automated reciprocator that moves in a uniform pattern to cover the surface of the substrate 32 with a uniform (or substantially uniform) amount of the reactant mixture. The use of a doctor blade is another technique that can be employed to apply the reactant mixture. In flow coating, a programmable dispenser is used to apply the reactant mixture.

Referring to FIG. 4, the substrate 32 is bonded to the aperture brace 22 via adhesive material 28, resulting in the structure shown in FIG. 5. In one embodiment, the adhesive material 28 is bonded to the aperture brace 22 before being bonded to the substrate 32. In another embodiment, the adhesive material 28 is bonded to the substrate 32 before being bonded to the aperture brace 22. In yet another embodiment, the adhesive material 28 is bonded to the substrate 32 and the aperture brace 22 simultaneously.

In embodiments where the adhesive material 28 is provided as a thermoplastic adhesive, the adhesive material 28 is bonded to the substrate 32 and the aperture brace 22 by melting the thermoplastic adhesive at, and subjecting the oleophobic low adhesion 20 coating 26 to, a bonding temperature and a bonding pressure. In one embodiment, the bonding temperature is at least about 290° C. In one embodiment, the bonding temperature can be at least about 310° C. In another embodiment, the bonding temperature can be at least about 325° C. In one embodiment, the bonding pressure is at least about 100 psi. In one embodiment, the bonding pressure can be at least about 300 psi.

After bonding the substrate 32 to the aperture brace 22, the aperture brace 22 may be used as a mask during one or more patterning processes to extend the apertures 22 a into the adhesive material 28, as shown in FIG. 2. The aperture brace 22 may also be used as a mask during one or more patterning processes to form nozzles 24 a in the substrate 32, thereby forming the nozzle plate 24 shown in FIG. 2. The one or more patterning processes used to form nozzles 24 a may also be applied to form nozzle openings 26 a within the oleophobic low adhesion coating 26, wherein the nozzle openings 26 a communicate with the nozzles 24 a. In one embodiment, the apertures 22 a may be extended into the adhesive material 28 by a laser ablation patterning process, or the like. In one embodiment, the nozzles 24 a and nozzle openings 26 a may be formed in the substrate 32 and the oleophobic low adhesion coating 26, respectively, by a laser ablation patterning process, or the like.

EXAMPLES

Synthesis of an Oleophobic Grafted Polymer (A). Referring to FIG. 6, a 17.5% solution of a fluoroelastomer (TECNOFLON® FKM (P 959), Solvay Specialty Polymers, Alpharetta, Ga.) was made by dissolving in methyl isobutyl ketone (MIBK) and about 1 pph by weight FC4430 (3M) and AKF 290 (Wacker). (Without being bound by theory, it is believed that the surfactant may impart compatibility between the fluoroelastomer and the release layer/oil applied on fuser and it prevents pin holes/fish eye defect.) Next, an amino crosslinker and FLUORLINK™ S10 (Solvay Specialty Polymers, Alpharetta, Ga.) with a mole ratio of 1.5:1 in MIBK were mixed and rolled overnight. It has been observed that keeping the mole ratio constant and increasing the amount of crosslinker and FLUORLINK™ S10 proportionally results in improved low adhesion properties. In this Example, three different formulations were tried with (1) crosslinker: and FLUORLINK™ S10 (0.86 mM:0.57 mM) (2) crosslinker: and FLUORLINK™ S10 (1.71 mM:1.13 mM) (3) crosslinker: and FLUORLINK™ S10 (2.56 mM:1.70 mM. After 16-18 h, Part B was added into Part A dropwise, as indicated in FIG. 3. Once the addition of Part B to Part A was done, MgO/CaO (9% stock solution in MIBK mixture in the sol was added and the mixture shaked vigorously for five minutes using a devil shaker and the resulting mixture was poured into molds (6×6 inch) and kept at room temperature for 16-18 h. Part of the solution was draw bar coated on a polyimide substrate for surface property measurement. Those were cured at room temperature for overnight and transferred to an oven which was kept at 218° C. for 4 hours. Formulation (3) with increased amount of EF:FSL10 provided the best surface properties and was further evaluated for anti-wetting coating application

Characterization of the Oleophobic Grafted Polymer: TGA decomposition profile in air shows the coatings are stable until 330° C. (FIG. 7). Coatings were evaluated for surface properties towards hexadecane (which can be used as a surrogate for oil) and solid ink. Results are shown in Table 1 below.

TABLE 1 Contact Angle (Sliding Contact Angle (Sliding Angle) hexadecane(degree) Angle) solid ink (degree) Stacking Stacking + Stacking Stacking + Initial 290° C./ 2 day Initial 290° C./ 2 day (after 350 psi/ Inking at (after 350 psi/ Inking at Coating curing) 30 min 140° C. curing) 30 min 140° C. Example 64(12- 63 63(25- 68(15- 66 64(32- (A) 15) (20-23) 27) 19) (24-28) 35) Control 65(7- 63 N.A. 71 68 (15) 60 (20) Coating 11) (13-15) (10)

As can be seen, the surface properties are comparable to the current control coating. These coatings maintained high contact angles after stacking conditions (290° C./1350 PSI with Teflon coverlay) which simulates press adhesive bonding cycles employed during printhead fabrication. Also stacked coatings maintained high contact angle after 2 days at 140° C. with molten CYMK ink. The sliding angles were somewhat higher than a control, but the ink slid cleanly from the surface and it is believed to be sufficiently low to enable easy cleaning in use. In addition, this exemplary oleophobic grafted polymer is expected to have the mechanical robustness desired for the long term performance of these coatings. These coatings can be scaled up through flow coating procedures and the demonstration of the flow coating using these grafted polymers has been accomplished.

The fact that these coatings show no oil and have very high thermal stability while maintaining the desired surface properties makes them attractive options for anti-wetting coatings for high definition piezo print applications. 

What is claimed is:
 1. An oleophobic grafted polymer comprising: a crosslinked fluoroelastomer; and a perfluorinated polyether grafted to the crosslinked fluoroelastomer.
 2. The oleophobic grafted polymer of claim 1, wherein the fluoroelastomer is crosslinked with an aminofunctionalized silane.
 3. The oleophobic grafted polymer of claim 2, wherein the aminofunctionalized silane provides graft attachment points.
 4. The oleophobic grafted polymer of claim 2, wherein the aminofunctionalized silane comprises an aminoalkylsilane-modified polysiloxane.
 5. The oleophobic grafted polymer of claim 1, having a structure of formula I:

wherein FE is a fluoroelastomer; PFPE is a perfluorinated polyether; L is a linker; m, and o are independently an integer from 3 to 8; n is an integer from 1 to 10; each incidence of R¹ and R² is independently a substituted or unsubstituted C₁-C₆ alkyl, R³ and R⁴ are independently an optionally fluorinated C₁-C₆ alkyl or an optionally fluorinated C₁-C₆ alkoxy.
 6. The oleophobic grafted polymer of claim 5, wherein the linker L comprises a C₁-C₆ alkyl terminating in a functional group capable of covalently linking to a terminal hydroxyl functionality group of the perfluorinated polyether.
 7. The oleophobic grafted polymer of claim 5, wherein the fluoroelastomer (FE) is a polymer comprising a monomer unit selected from the group consisting of vinylidene fluoride, tetrafluorethylene, hexafluoropropylene, perfluoromethylvinylether and combinations thereof.
 8. The oleophobic grafted polymer of claim 5, wherein the fluoroelastomer (FE) has a fluorine content of at least about 65 percent.
 9. The oleophobic grafted polymer of claim 5, wherein the fluoroelastomer (FE) has a molecular weight in a range from about 50,000 to about 70,0000 daltons as measured by gel permeation chromatography.
 10. The oleophobic grafted polymer of claim 5, wherein the perfluorinated polyether (PFPE) is an alkoxysilane-terminated perfluorinated polyether having an average molecular weight in a range from about 1,500 daltons to about 2,500 daltons.
 11. A process for making an oleophobic grafted polymer comprising: crosslinking a fluoroelastomer with an aminofunctionalized silane; and grafting an alkoxysilane-terminated perfluorinated polyether to the crosslinked fluoroelastomer.
 12. The process of claim 11, wherein the the oleophobic grafted polymer has a final structure of formula I:

wherein FE is a fluoroelastomer; PFPE is a perfluorinated polyether; L is a linker; m, n, and o are independently an integer from 1 to 10 each incidence of R¹ and R² is independently an optionally fluorinated C₁-C₆ alkyl, R³ and R⁴ are independently an optionally fluorinated C₁-C₆ alkyl or an optionally fluorinated C₁-C₆ alkoxy.
 13. The process of claim 11, wherein the crosslinking step is performed in the presence of the alkoxysilane-terminated perfluorinated polyether.
 14. The process of claim 13, wherein a ratio of the aminofunctionalized silane to the alkoxysilane-terminated perfluorinated polyether is in a range from about 0.5:1 to about 3:1.
 15. The process of claim 13, wherein an amount of the aminofunctionalized silane relative to the fluoroelastomer is in a range from about 2 pph to about 10 pph.
 16. The process of claim 11, wherein the fluoroelastomer (FE) is a polymer comprising a monomer unit selected from the group consisting of vinylidene fluoride, tetrafluorethylene, hexafluoropropylene, perfluoromethylvinylether and combinations thereof.
 17. The process of claim 11, wherein the fluoroelastomer (FE) has a fluorine content of at least about 65 percent.
 18. The process of claim 11, wherein the fluoroelastomer (FE) has a molecular weight in a range from about 50,000 to about 70,0000 daltons as measured by gel permeation chromatography.
 19. The process of claim 11, wherein the perfluorinated polyether (PFPE) is an alkoxysilane-terminated perfluorinated polyether having an average molecular weight in a range from about 1,500 daltons to about 2,500 daltons.
 20. An oleophobic grafted polymer comprising: a crosslinked fluoroelastomer of structure A:

wherein n is an integer from 1-10; each of R₁ and R₂ are independently an optionally fluorinated C₁-C₆ alkyl; and a perfluorinated polyether grafted to the crosslinked fluoroelastomer; wherein the OCH₃ groups of the polysiloxane crosslinker provide the reactive site for grafting the perfluorinated polyether. 